Azo-dyestuffs and process of making same



Patented Aug. 6, 1935 PATENT OFFICE 3,010,746. g AZO-DYESTUFFS AND rnoonss OF MAKING SAME Grald Bonhote and Jakob Danuser, Basel. Switzerland, assignors to the firm of Society of Chemical Industry in Basle, Basel, Switzerland No Drawing.

Application January 23, 1935,

Serial No. 3,191. In Switzerland January 30,'

9 Claims, (01. 260-95) This invention relates to the manufacture of new dyestuffs which are characterized by the brilliancy of their dyeings and other valuable dyeing properties, by coupling adiazo-compound 6 derived from an amine of the general formula i so;

in which X represents alkyl, aralkyl or aryl and Y represents alkyl, with a coupling component. According to the choice of the coupling component, various dyestuffs are obtained. These new dyestuffs correspond to the general formula O=COY ton dyestuffsv are obtained; whereas with nonsulfonated coupling components, pigment dyestufis are obtained. Such non-sulfonated coupling components are the arylides of acetoacetic acid, benzoylacetic acid or terephthaloyl-bis-acetic acid; also arylides of carboxylic acids of hydroxybenzenes, hydroxynaphthalenes, hydroxycarbazoles, hydroxynaphthocarbazoles, hydroxyanthracenes and hydroxyphenanthrenes. Such arylides are described in large number in the pertinent literature. Particularly valuable are the dyeings produced on the fibre by means of these,- said non-sulfonated coupling components, par ticularly those obtained with the arylides of 2,3-

hydroxynaphthoic acid. The dyestuffs thus obtained correspond to the general formula in which R represents an aromatic radical of the benzene or naphthalene series, and X and Y have the meaning already indicated above, and dye the animal fiber vivid orange to scarlet tints which are characterized by their purity and very good properties of fast ness. When dry they are red to orange colored powders which are insoluble inwater. i 1

TheT-following examples illustrate the'invention:-- A l r V Example 1 30.5 parts by Weight of theethylester of 2- amino-i-carboxylic nylsulfone are diazotized in the usual manner. The clear diazo-solution thus obtained is introduced into a solution consisting of 29.7 parts of 2,3-hydroxynaphthoic acid-orthochloranilide, 60 parts of sodium hydroxide solution of 30 per cent. strength 15 parts of sodium carbonate and 2000 parts of water. The dyestufi formed is precipitated immediately; the orange precipitate is filtere'dand dried. The new dyestuff very probably corresponds to the formula H I NH o=c -o,H,

O C=O V v. U01 Similar dyestuffs are obtained by substituting other esters, for instance methylester, butylester, propylester or isopropylester for the ethylester of 2-amino-4-carboxylic acid-4'-methy1-1,1'-diphenylsulfone.

Example 2 7. Cotton y i rnv i s grounded with a solution of 7 acid-4' methyl- 1,1- diphegrams of the 2,3-hydroxynaphthoic acid-metatoluidide in 300 cc. of hot water, to which has een added 12 cc. of sodium hydroxide solution of 30 per cent. strength, 10 cc. of Turkey red oil and water to, make 1 litre. The yarnis then wrung out and developed in a diaz'o-solution; buifered with sodium acetate, and containing per litre the diam-compound corresponding with 2 grams of the ethyl-ester of 2-amino-4-carboxylic naphthalide or the 3,4-dichloranilide of 2,3-hydroxynaphthoic acid.

Yellow orange tints are obtained with the ortho- Iand meta-toluidides, the orthoand meta-chloroanilides and the 2,5-dichloranilide.

Example 4 The fabric to be printed is foularded with an alkaline solution containing per litre 14 grams of acid-4'methyl-1,l'-diphenylsulfone. There is produced a pure orange of excellent properties of i i iwf i i 't t l fastness. Therefore the new dyestuff very prob- IS plmed with P m Color coflmmmg (b1 corresponds to the formula per kilo 12 grams of diazotized ethylester of 2- y amino-4carboXy1ic acid 1,1 diphenylsulfone.

15 The deep, pure orange dyeing develops very quickly and is of excellent fastness. Therefore,

the new dyestuff very probably corresponds to the formula Similar orange tints are obtained, for instance, with the anilide, the para-chloranilide, the orthoanisidide, the para-toluidide, the meta-nitrani= hole, the 5-chloro-2-toluidide, the meta-chloram. ilide, the 3,4-dichloranilide, the m eta-xylidide of the 2,3-hydroxynaphthoic acid. Scarlet tints are obtained with the anaphthalide of the 2,3-hydroxynaphthoic acid.

para-chloranilides, the para-toluidide, the metanitranilide, the 5-chloro-2-toluidide and the 3,4-

dichloranilide, the [i-naphthalide, the orthoand para-anisidide and the para-phenetidide of 2,3- hydroxynaphthoic acid.

If in the foregoing examples the specified arylide of 2,3-hydroxynaphthoic acid is exchanged for, say, the di-(acetoacetyl)-ortho-ortho-tolidide, the terephthaloyl-bis-(acetic acid-ZA-dimethoxy-5-chloroanilide), the benzoyl-acetic acid-ortho-chlor-amlide, pure yellow tints are obtained of excellent properties of fastness.

What We claim is:

1. The azo-dyestuffs of the general formula 4o Example 3 Cotton yarn is impregnated with a solution of 5.5 grams of 2,3-hydroxynaphthoic acid-para chloranilide, 12 cc. of sodium hydroxide solution .of 30 per cent. strength and 10 cc. of Turkey red oil. After being wrung out, the dyestuff is de' veloped by means of a diaZo-solution, buffered with sodium acetate and containing the diazocompound corresponding with 2 grams of the .ethylester of 2-arnino-4-carboxylic acid-4- chloro-1,1-diphenylsulfone, per litre. The yarn is then rinsed and soaped. A very pure orange 1 l tint is obtained which has very good properties of fastness. Therefore, the new dyestuff very probably corresponds to the formula in which X represents aryl, Y represents alkyl I and R represents the radical of a coupling com- 3 ponent.

I h 2. The azo-dyestufis of the general formula r 2!: Q HO (13:0

NH o=oo ones I o=ooY I 1 in which X represents aryl, Y represents alkyl 5 Similar tints are obtained with other arylides and; R'represents the radical of an unsulfonated of ZB-hydroxynaphthoici acid, for instance'the [3-- coupling component.

Like tints are obtained with the metaand 3. The azo-dyestufis of the general formula HO (i=0 in which X represents aryl and R represents an aromatic nucleus of the benzene or naphthalene series, which products are red to orange colored powders insoluble in water and dyeing cotton vivid yellow-orange to scarlet tints of very good properties of fastness.

5. The azo-dyestuffs of the general formula in which R. represents an aromatic nucleus of the benzene or naphthalene series, which products are red to orange colored powders insoluble in water and dyeing cotton vivid yellow-orange to scarlet tints of very good properties of fastness.

6. The azo-dyestufis of the general formula.

in which R. represents an aromationucleus of the benzene series, which products are red to orange colored powders insoluble in water and dyeing cotton vivid yellow-orange to scarlet tints of very good properties of fastness.

7. The azo-dyestufi of the formula which represents an orange colored powder insoluble in water and dyeing cotton vivid orange tints of very good properties of fastness.

8. The azo-dyestufi of the formula which represents an orange colored powder insoluble in water and dyeing cotton vivid orange tints of very good properties of fastness.

9. The azo-dyestuff of the formula SIO: ON=N F 1 ll which represents an orange colored powder insoluble in water and dyeing cotton vivid orange tints of very good properties of fastness.

GERALD BoNHoTE.

JAKOB DANUSER. 

